CN113975939A - Decarbonization method of Fischer-Tropsch synthesis tail gas - Google Patents
Decarbonization method of Fischer-Tropsch synthesis tail gas Download PDFInfo
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- CN113975939A CN113975939A CN202010730590.9A CN202010730590A CN113975939A CN 113975939 A CN113975939 A CN 113975939A CN 202010730590 A CN202010730590 A CN 202010730590A CN 113975939 A CN113975939 A CN 113975939A
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- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 39
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 39
- 238000005262 decarbonization Methods 0.000 title claims abstract description 13
- 230000008929 regeneration Effects 0.000 claims abstract description 42
- 238000011069 regeneration method Methods 0.000 claims abstract description 42
- 238000010521 absorption reaction Methods 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 81
- 238000001704 evaporation Methods 0.000 claims description 46
- 230000008020 evaporation Effects 0.000 claims description 46
- 238000005406 washing Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002737 fuel gas Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000005261 decarburization Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1425—Regeneration of liquid absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1475—Removing carbon dioxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method for decarbonizing Fischer-Tropsch synthesis tail gas, and belongs to the technical field of tail gas decarbonization. The method for decarbonizing the Fischer-Tropsch synthesis tail gas comprises the following steps: step 1: CO 22Absorption treatment; step 2: and (5) carrying out solvent regeneration treatment. The method for decarbonizing the Fischer-Tropsch synthesis tail gas can reduce the loss of hydrocarbons in the decarbonization process, can reduce the regeneration heat consumption, can improve the purity of the regenerated gas, has large treatment capacity, is simple to operate, has wide market prospect, and is suitable for large-scale popularization and application.
Description
Technical Field
The invention relates to a method for decarbonizing Fischer-Tropsch synthesis tail gas, and belongs to the technical field of tail gas decarbonization.
Background
The Fischer-Tropsch synthesis process is the core part of the coal-to-liquid process. The content of hydrocarbon in the recycle gas after oil products are separated from the Fischer-Tropsch synthesis reactor is 15 to 32 percent, and CO is2In an amount of up to 30%, especially when iron-based catalysts are used, olefins and C4The above heavy paraffins are relatively abundant and contain a small amount of oxygen-containing organic substances such as aldehydes, ketones, alcohols, and acids.
The main function of the decarbonization unit is to decarbonize the tail gas discharged from the Fischer-Tropsch synthesis loop of the high-temperature slurry bed, so the process is different from other decarbonization occasions in process selection, and the main reason is that the Fischer-Tropsch synthesis tail gas contains a small amount of oxygen-containing compounds and saturated light oil components, which easily causes pollution to a solvent and complication of the process. Aiming at the physical distribution characteristics and the process requirements, the decarburization process technology required to be adopted has the following characteristics: (1) the decarburization process should prevent light oil from entering the decarburization system as much as possible; (2) the damage effect of a small amount of oxygen-containing compounds in the stream on the decarbonization solvent is avoided; (3) has high decarburization selectivity and can effectively reduce the loss of hydrocarbons.
The existing decarbonization method of the Fischer-Tropsch synthesis tail gas has the defects of low processing capacity, high regeneration energy consumption, low purification degree, low purity of regenerated gas and the like. In view of the above, there is a need to provide a method for decarbonizing fischer-tropsch synthesis tail gas to overcome the deficiencies of the prior art.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for decarbonizing Fischer-Tropsch synthesis tail gas. The method for decarbonizing the Fischer-Tropsch synthesis tail gas can reduce the loss of hydrocarbons in the decarbonization process, reduce the regeneration heat consumption, improve the purity of the regenerated gas and have large treatment capacity.
The technical scheme for solving the technical problems is as follows: a method for decarbonizing Fischer-Tropsch synthesis tail gas comprises the following steps:
step 1: CO 22Absorption treatment
Washing Fischer-Tropsch synthesis tail gas, then exchanging heat with barren solution, heating to a temperature of more than or equal to 90 ℃, entering the bottom of an absorption tower, and making countercurrent contact with cold barren solution and hot barren solution entering the tower from the top of the absorption tower and semi-barren solution entering the tower from the middle of the absorption tower until CO in the tail gas is2The content is less than or equal to 1.5 wt%, the mixture is cooled to be less than or equal to 50 ℃, the mixture enters a purification gas separator and is in countercurrent contact with washing water, the obtained condensed water is sent to a pregnant solution flash evaporation tank and an underground tank, part of purified gas returns to a Fischer-Tropsch synthesis unit, and the rest of purified gas is sent to a low-temperature oil washing unit;
step 2: solvent regeneration treatment
Carrying out primary flash evaporation on condensed water in the pregnant solution flash evaporation tank, washing the obtained primary flash evaporation gas with washing water, and then sending the washed gas to a fuel gas pipe network, and feeding the obtained pregnant solution into a flash evaporation section at the top of a pressurized regeneration tower for secondary flash evaporation;
part of the rich solution obtained by the secondary flash evaporation enters the stripping sections at the top and the middle part of the normal pressure regeneration tower, and the other part of the rich solution flows into the bottom of the normal pressure regeneration tower, and enters a lean solution flash drum after being regenerated to form a lean solution;
and (4) feeding the stripping steam flashed from the barren solution flash tank into the bottom of the normal-pressure regeneration tower, feeding barren solution into a barren solution pump, and feeding semi-barren solution into a semi-barren solution pump.
The method for decarbonizing the Fischer-Tropsch synthesis tail gas has the beneficial effects that:
1. the method for decarbonizing the Fischer-Tropsch synthesis tail gas has the hydrocarbon loss of about 0.8 percent. In the prior art, the decarbonization is carried out by an amine method, and the loss of hydrocarbons is about 1.2 percent; physical solvent process, loss of hydrocarbons is about 100%; the loss of hydrocarbons was about 9.9% with the mixed solvent process. Therefore, the present invention can reduce the loss of hydrocarbons during the decarburization process.
2. According to the method for decarbonizing Fischer-Tropsch synthesis tail gas, the solution regeneration energy consumption is lower than 74.9kJ/mol CO2. In the prior art Benfield catalytic hot potassium carbonate decarbonization method, the solution regeneration heat consumption is about 112.36kJ/mol CO2. Therefore, the present invention can reduce the regeneration heat consumption.
3. The method for decarbonizing the Fischer-Tropsch synthesis tail gas can improve the purity of the regenerated gas, has large treatment capacity, is simple to operate, has wide market prospect, and is suitable for large-scale popularization and application.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, in step 1, the washing is performed in a circulating gas water washing column.
The adoption of the further beneficial effects is as follows: in the circulating gas water washing tower, the oxygen-containing organic matters in the tail gas can be washed.
Further, in step 1, a purified air cooler is used for cooling.
The adoption of the further beneficial effects is as follows: the tail gas can be cooled to less than or equal to 50 ℃ by adopting a purified gas air cooler.
Further, in the step 1, the pressure of the primary flash evaporation is 0.3 MPa.
The adoption of the further beneficial effects is as follows: by adopting the pressure parameters, primary flash evaporation can be carried out, and most of the obtained primary flash evaporation gas is CO and H2And hydrocarbon gases.
Further, in the step 2, the pressure of the secondary flash evaporation is 0.1 MPa.
The adoption of the further beneficial effects is as follows: by adopting the pressure parameters, secondary flash evaporation can be carried out, and most of the obtained secondary flash evaporation gas is CO2And water vapor.
Further, in step 2, the pressure of the stripping steam is 0.022MPa, and the temperature is 105 ℃.
Further, in the step 2, steam boilers are arranged at the bottoms of the pressurizing regeneration tower and the normal pressure regeneration tower.
Detailed Description
The principles and features of this invention are described below in conjunction with specific embodiments, which are set forth merely to illustrate the invention and are not intended to limit the scope of the invention.
Example 1
The method for decarbonizing the Fischer-Tropsch synthesis tail gas comprises the following steps:
step (ii) of1：CO2Absorption treatment
Washing Fischer-Tropsch synthesis tail gas in a circulating gas water washing tower, then exchanging heat with barren solution, heating to 90 ℃, entering the bottom of an absorption tower, counter-currently contacting with cold barren solution and hot barren solution entering the tower from the top of the absorption tower and semi-barren solution entering the tower from the middle of the absorption tower, and waiting for CO in the tail gas2The content is 1.5 wt%, then the mixture is cooled to 50 ℃ by a purified gas air cooler, enters a purified gas separator and is in countercurrent contact with washing water, the obtained condensed water is sent to a pregnant solution flash tank and an underground tank, part of the purified gas returns to a Fischer-Tropsch synthesis unit, and the rest of the purified gas is sent to a low-temperature oil washing unit.
Step 2: solvent regeneration treatment
And carrying out primary flash evaporation on the condensed water in the pregnant solution flash evaporation tank under the pressure of 0.3MPa, washing the obtained primary flash evaporation gas with washing water, sending the washed primary flash evaporation gas to a fuel gas pipe network, feeding the obtained pregnant solution into a flash evaporation section at the top of the pressurization regeneration tower, and carrying out secondary flash evaporation under the pressure of 0.1 MPa.
And (3) allowing part of the rich solution obtained by the secondary flash evaporation to enter the stripping sections at the top and the middle part of the normal pressure regeneration tower, allowing the other part of the rich solution to flow into the bottom of the normal pressure regeneration tower, regenerating to form a barren solution, and allowing the barren solution to enter a barren solution flash evaporation tank.
And (3) feeding the stripping steam flashed from the barren solution flash tank into the bottom of the normal-pressure regeneration tower under the pressure of 0.022MPa and the temperature of 105 ℃, feeding barren solution into a barren solution pump, and feeding semi-barren solution into a semi-barren solution pump. The bottoms of the pressurized regeneration tower and the normal pressure regeneration tower are respectively provided with a steam boiler.
Example 2
The method for decarbonizing the Fischer-Tropsch synthesis tail gas comprises the following steps:
step 1: CO 22Absorption treatment
Washing Fischer-Tropsch synthesis tail gas in a circulating gas water washing tower, then exchanging heat with barren solution, heating to 92 ℃, entering the bottom of an absorption tower, counter-currently contacting with cold barren solution and hot barren solution entering the tower from the top of the absorption tower and semi-barren solution entering the tower from the middle of the absorption tower, and waiting for CO in the tail gas2The content is 1.4 wt%, andand cooling the purified gas to 49 ℃ by adopting a purified gas air cooler, then feeding the cooled purified gas into a purified gas separator, and after the purified gas is in countercurrent contact with washing water, sending the obtained condensed water to a pregnant solution flash tank and an underground tank, returning a part of the purified gas to the Fischer-Tropsch synthesis unit, and sending the rest of the purified gas to the low-temperature oil washing unit.
Step 2: solvent regeneration treatment
And carrying out primary flash evaporation on the condensed water in the pregnant solution flash evaporation tank under the pressure of 0.3MPa, washing the obtained primary flash evaporation gas with washing water, sending the washed primary flash evaporation gas to a fuel gas pipe network, feeding the obtained pregnant solution into a flash evaporation section at the top of the pressurization regeneration tower, and carrying out secondary flash evaporation under the pressure of 0.1 MPa.
And (3) allowing part of the rich solution obtained by the secondary flash evaporation to enter the stripping sections at the top and the middle part of the normal pressure regeneration tower, allowing the other part of the rich solution to flow into the bottom of the normal pressure regeneration tower, regenerating to form a barren solution, and allowing the barren solution to enter a barren solution flash evaporation tank.
And (3) feeding the stripping steam flashed from the barren solution flash tank into the bottom of the normal-pressure regeneration tower under the pressure of 0.022MPa and the temperature of 105 ℃, feeding barren solution into a barren solution pump, and feeding semi-barren solution into a semi-barren solution pump. The bottoms of the pressurized regeneration tower and the normal pressure regeneration tower are respectively provided with a steam boiler.
Example 3
The method for decarbonizing the Fischer-Tropsch synthesis tail gas comprises the following steps:
step 1: CO 22Absorption treatment
Washing Fischer-Tropsch synthesis tail gas in a circulating gas water washing tower, then exchanging heat with barren solution, heating to 92 ℃, entering the bottom of an absorption tower, counter-currently contacting with cold barren solution and hot barren solution entering the tower from the top of the absorption tower and semi-barren solution entering the tower from the middle of the absorption tower, and waiting for CO in the tail gas2The content is 1.3 wt%, then the mixture is cooled to 48 ℃ by a purified gas air cooler, enters a purified gas separator and is in countercurrent contact with washing water, the obtained condensed water is sent to a pregnant solution flash tank and an underground tank, part of the purified gas returns to a Fischer-Tropsch synthesis unit, and the rest of the purified gas is sent to a low-temperature oil washing unit.
Step 2: solvent regeneration treatment
And carrying out primary flash evaporation on the condensed water in the pregnant solution flash evaporation tank under the pressure of 0.3MPa, washing the obtained primary flash evaporation gas with washing water, sending the washed primary flash evaporation gas to a fuel gas pipe network, feeding the obtained pregnant solution into a flash evaporation section at the top of the pressurization regeneration tower, and carrying out secondary flash evaporation under the pressure of 0.1 MPa.
And (3) allowing part of the rich solution obtained by the secondary flash evaporation to enter the stripping sections at the top and the middle part of the normal pressure regeneration tower, allowing the other part of the rich solution to flow into the bottom of the normal pressure regeneration tower, regenerating to form a barren solution, and allowing the barren solution to enter a barren solution flash evaporation tank.
And (3) feeding the stripping steam flashed from the barren solution flash tank into the bottom of the normal-pressure regeneration tower under the pressure of 0.022MPa and the temperature of 105 ℃, feeding barren solution into a barren solution pump, and feeding semi-barren solution into a semi-barren solution pump. The bottoms of the pressurized regeneration tower and the normal pressure regeneration tower are respectively provided with a steam boiler.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. The method for decarbonizing Fischer-Tropsch synthesis tail gas is characterized by comprising the following steps of:
step 1: CO 22Absorption treatment
Washing Fischer-Tropsch synthesis tail gas, then exchanging heat with barren solution, heating to a temperature of more than or equal to 90 ℃, entering the bottom of an absorption tower, and making countercurrent contact with cold barren solution and hot barren solution entering the tower from the top of the absorption tower and semi-barren solution entering the tower from the middle of the absorption tower until CO in the tail gas is2The content is less than or equal to 1.5 wt%, the mixture is cooled to be less than or equal to 50 ℃, the mixture enters a purification gas separator and is in countercurrent contact with washing water, the obtained condensed water is sent to a pregnant solution flash evaporation tank and an underground tank, part of purified gas returns to a Fischer-Tropsch synthesis unit, and the rest of purified gas is sent to a low-temperature oil washing unit;
step 2: solvent regeneration treatment
Carrying out primary flash evaporation on condensed water in the pregnant solution flash evaporation tank, washing the obtained primary flash evaporation gas with washing water, and then sending the washed gas to a fuel gas pipe network, and feeding the obtained pregnant solution into a flash evaporation section at the top of a pressurized regeneration tower for secondary flash evaporation;
part of the rich solution obtained by the secondary flash evaporation enters the stripping sections at the top and the middle part of the normal pressure regeneration tower, and the other part of the rich solution flows into the bottom of the normal pressure regeneration tower, and enters a lean solution flash drum after being regenerated to form a lean solution;
and (4) feeding the stripping steam flashed from the barren solution flash tank into the bottom of the normal-pressure regeneration tower, feeding barren solution into a barren solution pump, and feeding semi-barren solution into a semi-barren solution pump.
2. The method for decarbonizing Fischer-Tropsch synthesis tail gas of claim 1, wherein the washing is performed in a circulating gas washing tower in the step 1.
3. The method for decarbonizing Fischer-Tropsch synthesis tail gas of claim 1, wherein in the step 1, a purified air cooler is adopted for cooling.
4. The method for decarbonizing Fischer-Tropsch synthesis tail gas of claim 1, wherein in the step 1, the pressure of the primary flash evaporation is 0.3 MPa.
5. The method for decarbonizing Fischer-Tropsch synthesis tail gas of claim 1, wherein in the step 2, the pressure of the secondary flash evaporation is 0.1 MPa.
6. The method for decarbonizing Fischer-Tropsch synthesis tail gas of claim 1, wherein in the step 2, the pressure of the stripping steam is 0.022MPa, and the temperature is 105 ℃.
7. A Fischer-Tropsch synthesis tail gas decarbonization method according to any one of claims 1 to 6, characterized in that in the step 2, steam boilers are arranged at the bottoms of the pressurized regeneration tower and the atmospheric regeneration tower.
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|---|---|---|---|---|
| CN101210186A (en) * | 2006-12-26 | 2008-07-02 | 南化集团研究院 | Solvent and method for removing carbon dioxide from Fischer-Tropsch synthesis circulation gas |
| CN103768895A (en) * | 2012-10-23 | 2014-05-07 | 中国石油化工股份有限公司 | Method for low-energy consumption removal of carbon dioxide by hot potash |
| US20150135960A1 (en) * | 2012-07-20 | 2015-05-21 | Mitsubishi Heavy Industries, Ltd. | Co2 recovery system |
| CN105838465A (en) * | 2016-05-20 | 2016-08-10 | 北京中科瑞奥能源科技股份有限公司 | Process and system for preparing liquefied natural gas by utilizing Fischer-Tropsch synthesis tail gas |
| CN110684574A (en) * | 2018-07-06 | 2020-01-14 | 中国石油化工股份有限公司 | Decarbonization method for preparing liquefied natural gas from high-carbon-content natural gas |
-
2020
- 2020-07-27 CN CN202010730590.9A patent/CN113975939A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210186A (en) * | 2006-12-26 | 2008-07-02 | 南化集团研究院 | Solvent and method for removing carbon dioxide from Fischer-Tropsch synthesis circulation gas |
| US20150135960A1 (en) * | 2012-07-20 | 2015-05-21 | Mitsubishi Heavy Industries, Ltd. | Co2 recovery system |
| CN103768895A (en) * | 2012-10-23 | 2014-05-07 | 中国石油化工股份有限公司 | Method for low-energy consumption removal of carbon dioxide by hot potash |
| CN105838465A (en) * | 2016-05-20 | 2016-08-10 | 北京中科瑞奥能源科技股份有限公司 | Process and system for preparing liquefied natural gas by utilizing Fischer-Tropsch synthesis tail gas |
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